JOURNAL OF ALLOYS AND COMPOUNDS
·
2022
·
IF 6.371
Yue Yin,Xian Luo,Benjun Xu
Li 4 Ti 5 O 12 (LTO) is the most promising anode material for lithium-ion batteries owing to its excellent cycle stability and safety. However, the electrochemical performance of LTO at high rates is limited by its low conductivity. Generally, LTO preparation requires organic titanium sources, which are expensive. In this study, inexpensive H 2 TiO 3 was used as the titanium source, LiOH‧H 2 O served as the lithium source, and NH 3 ‧H 2 O was added to control the pH of the solution. Simple one-step liquid-phase deposition and calcination were performed for obtaining in situ self-assembled LTO submicron spheres with stable morphology and excellent electrochemical performance. According to electrochemical performance tests, the sample calcined with 4 mL of 25% NH 3 ‧H 2 O at 700 °C (LTO-4–700) exhibited the best performance. Its discharge capacity remained at 176.4 mAh g −1 over 100 cycles at 87.5 mA g −1 and retained at 136.7 mAh g −1 over 500 cycles at 875 mA g −1 , and its specific capacity was 105.6 mAh g −1 over 1000 cycles, even at a current of 1750 mA g −1 with a retention rate of 96.7%. Furthermore, LTO-4–700 exhibited excellent rate performance at 3500 mA g −1 compared to other samples. Cyclic voltammetry and electrochemical impedance spectroscopy confirmed that submicron spherical LTO-4–700 had a high Li + migration rate and low electrochemical impedance.
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CHEMICAL ENGINEERING JOURNAL
·
2023
·
IF 15.1
Kang-Hui Hu,Chao-Qiong Zhu,Bao-Ping Zheng,Lang Qiu,Fang Wan,Yang Song,Ben-He Zhong,Zhen-Guo Wu,Xiao-Dong Guo
Li-rich Mn-based oxide cathodes are one of the most promising cathode candidates for high energy density over 400 Wh kg −1 , deriving from oxygen redox of Li-O-Li configuration. However, the deep oxygen oxidation would lead to the formation of peroxides and superoxides (O 2 n − , 0 < n ≤ 2) and even oxygen (O 2 ), accompanied by crystal phase transformation and structure collapse. Herein, an integrative strategy of simultaneously regulating the right amount of oxygen vacancies (OVs) and B-atom doping is proposed to achieve differentially modification of both R-3 m and C2/m phases. Firstly, Rietveld refinement, HRTEM and in situ XRD results reveal that the linear increase of OVs content is achieved by regulating the amount of BN and the selective introduction of OVs inside the C2/m phase makes the oxygen partial pressure lower in the weak O-Li-O bonds of TM-layer and inhibits oxygen release at over 4.5 V. Meanwhile, kinetics test shows oxygen defects would accelerate the Li + diffusion and reduce the electronic impedance driven by uneven local charge distribution. Secondly, lattice analysis shows the strong covalent B-O bonds located at the tetrahedral site not only prevent the overoxidation of the oxygen atoms at high voltage, but also hinder the migration of Mn atoms through tetrahedral sites, which effectively avoids the damage of the crystal structure. As a result, the modified cathode exhibits the excellent discharge specific capacity of 272 mA h g −1 at 0.1C, higher rate performance of 145 mA h g −1 at 5C, an outstanding capacity retention rate of 93% at 1C and lower voltage decay value of 0.43 V after 200 cycles. This promising strategy could simultaneously achieve both high energy density and superior cycling stability and help to advance industrial application of Li-rich Mn-based Cathodes.
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ACS Applied Materials & Interfaces
·
2023
·
IF 9.5
Zhichuan Bai,Xiang Gao,Zheng Liu,Dongliang Chao,Yingying Wang,Jie Yin,Cairong Jiang,Wenge Yang,Jianjun Ma,Yongjin Chen
Graphite is one of the major anode materials for commercial lithium-ion batteries. Li+ transport in a single graphite granule along intra and interlayer modes is a crucial factor for the battery performance. However, direct evidence and visualized details of the Li+ transports are hardly provided. Here, we report the direct observation of the anisotropic transport behavior of Li+ and investigate the electro-chemo-structure evolution during the lithiation of graphite through both the intra and interlayer pathways via in situ transmission electron microscopy. The in situ experiments of nano batteries give two extreme conditions, in which thermal runaway induced by polarization only occurs along the interlayer, not along the intralayer. The high diffusion energy barrier induced large polarization when the interlayer Li+ transport became dominant. The energy of the polarization electric field would be instantaneously released like a short electric pulse, which generated a substantial amount of joule heat and created an extremely high temperature, causing the melting of the tungsten tip. We provide another possible fundamental mechanism of thermal failure in graphite-based Li-ion batteries and hope this insightful work would help the safety management of graphite-based lithium-ion batteries.
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OPTICAL MATERIALS
·
2021
·
IF 3.08
Panpan Du,Qi Zhu,Xiaodong Li,Xudong Sun,Byung-Nam Kim,Ji-Guang Li
A series of garnet-type Li 6 CaLa 2(1- x ) Nb 2 O 12 : x RE phosphors (LCLN: x RE, RE = Pr, Sm, Tb and Dy) were prepared via sol-gel processing and subsequent calcination for the first time, with the course of phase evolution and the characteristics of the LCLN host and RE 3+ luminescence being investigated in detail. It was found that ∼900–1000 °C is a suitable temperature for precursor calcination to produce the garnet phase and LCLN has a relatively low phonon energy (∼725 cm −1 ) and a relatively wide bandgap (∼4.53 eV) for luminescence. The LCLN:0.012Pr, LCLN:0.04Sm, LCLN:0.06 Tb and LCLN:0.06Dy typical phosphors were analyzed to have dominant excitation/emission bands at ∼278/489, 265/614, 268/549 and 264/581 nm, emission colors of white, orange, green and yellowish white, and fluorescence lifetimes of ∼0.43, 0.74, 0.90 and 0.44 ms, respectively. Temperature-dependent photoluminescence found that the four phosphors maintained ∼28, 37, 45 and 56% of their room-temperature intensities at 423 K, with activation energies for thermal quenching of ∼0.37, 0.29, 0.34 and 0.25 eV, respectively. The results demonstrated that the Li-stuffed LCLN garnet could be a suitable host for UV excitable multicolor phosphors.
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ELECTROCHIMICA ACTA
·
2021
·
IF 6.901
Hongcheng Gao,Shihao Miao,Mengqin Shi,Xiaoxia Mao,Xiaojing Zhu
Low redox kinetics and shuttle effect of polysulfides (PSs) is a grand challenge for practical applications of lithium-sulfur (Li-S) batteries. Herein, cobalt (Co) nanoparticles embedded inside nitrogen (N)-doped hierarchical porous carbon (MgCo-HC) are prepared via one-pot approach. As a result, MgCo-HC unique structure with the large surface area and Co, N-doping is proposed for the strong physical/chemical adsorption of PSs, high conductivity, fast redox reaction kinetics and the high S utilization. The resultant S cathode delivers a high specific capacity of 1086.4 mA h/g at 0.1 C, low-capacity fading rate of 0.041% per cycle over 880 cycles at 2 C, and superior rate performance up to 5 C. More intriguingly, the S/MgCo-HC electrode delivers reversible area capacities of 5.1 and 5.5 mA h/cm 2 at 0.1 C under high S loading and learn electrolyte condition, respectively. Furthermore, the assembled Li-S soft-packaged battery is also readily assembled, which highlights stable electrochemical properties under folding conditions. This work provides a simple strategy to design advanced S hosts for the practical application of Li-S batteries with excellent electrochemical performance.
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Frontiers in Energy Research
·
2021
·
IF 4.008
Hu Lei,Yang Xulai,Chen Yumeng,Wang Lili,Li Jiajia,Tang Yujie,Zhang Haitao
TiNb2O7 (TNO) compound has been pursued tremendously due to its high theoretical capacity, high potential, and excellent cycle stability. Unfortunately, an intrinsic low electronic and ionic conductivity feature has restricted its broad applications in electrochemical energy storage fields. Two-dimensional (2D) nanostructures can effectively shorten Li-ion transport path and enhance charge transfer. Here, hierarchical structure TNO was constructed by using ethanol and acetic acid as particularly important organic chemicals of basic raw materials via a simple solvothermal reaction. Ethanol was found to play a critical role in the formation of 2D sheet structure. Meantime, reduced graphene oxide nanosheets can effectively improve electronic conductivity. As-obtained TiNb2O7 were wrapped further by graphene oxide nanosheets through a flocculation process. Their unique structure is beneficial to the final electrochemical performance. This study not only provides a general approach for the design of novel 2D nanomaterials wrapped by graphene because of the advantage of esterification reaction and flocculation reaction, but also improves the electronic and ionic conductivity simultaneously.
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CHEMICAL RESEARCH IN CHINESE UNIVERSITIES
·
2021
·Vol. 38
·期 1
·200-208
·
IF 1.307
Wang Yue,Wang Xiaoxue,She Ping,Guan Dehui,Song Lina,Xu Jijing
D esign and fabrication of functional porous air cathode materials with superior catalytic activity is still the key point for non-aqueous lithium-oxygen(Li-O 2 ) batteries. Herein, inspired by the self-standing three-dimensional(3D) structure of the natural spinach leaves, a unique binder-free and self-standing porous Au/spinach cathode for high-performance Li-O 2 batteries has been developed. The carbonized spinach leaves serve as a superconductive current collector and an ideal porous host for accommodating catalysts. The Au/spinach cathode could offer enough spaces for accommodating the discharge products, shorten the distance of the oxygen and electrolyte diffusion, and promote the oxygen reduction reaction(ORR) and oxygen evolution reaction (OER) processes. This optimized Au/spinach cathode achieved a high specific area capacity of 7.23 mA·h/cm 2 at a current density of 0.05 mA/cm 2 and exhibited excellent stability(280 cycles at 0.05 mA/cm 2 with a fixed capacity of 0.2 mA·h/cm 2 ). The superior performance encourages the construction of more advanced cathode architectures by the use of bio-composites for Li-O 2 batteries.
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INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES
·
2023
·
IF 8.2
Chaoqun Zhang,Qi He,Wenbin Luo,Jian Du,Yehan Tao,Jie Lu,Yi Cheng,Haisong Wang
The commercial graphene for Li ion batteries (LIBs) has high cost and low capacity. Therefore, it is necessary to develop a novel carbon anode. The cellulose nanowires (CNWs), which has advantages of low cost, high carbon content, is thought as a good carbon precursor. However, direct carbonization of CNWs leads to low surface area and less mesopores due to its easy aggregation. Herein, the metal-organic frameworks (MOFs) have been explored as templates to prepare porous carbon due to their 3D open pore structures. The porous carbon was developed with the coordination effect of CNWs and MOFs. The precursor of MOFs coordinates with the −OH and − COOH groups in the CNWs to provide stable structure. And the MOFs was grown in situ on CNWs to reduce aggregation and provide higher porosity. The results show that the porous carbon has high specific capacity and fast Li + /electronic conductivity. As anode for LIBs, it displays 698 mAh g −1 and the capacity retention is 85 % after 200 cycles. When using in the full-battery system, it exhibits energy density of 480 Wh kg −1 , suggesting good application value. This work provides a low-cost method to synthesize porous carbon with fast Li + /electronic conductivity for high-performance LIBs.
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Journal of Materials Chemistry A
·
2023
·Vol. 11
·期 43
·23342-23353
·
IF 11.9
Zhihui Ma,Jie Shi,Di Wu,Dishuang Chen,Shuai Shang,Xuanhui Qu,Ping Li
The sulfide-based solid electrolyte (SSE) has been considered as a strong candidate for potential uses in all-solid-state lithium batteries (ASSLBs). Nevertheless, most of the reported SSEs are plagued with their intrinsic air-sensitive behaviors and Li-incompatibility, which largely preclude scalable fabrication and widespread practical application. Herein, we report the Li6+xSb1−xSnxS5I (LSSSI-x) SSEs using nontoxic inexpensive Sn substitution to deal with these issues. The ionic conductivity of Li6+xSb1−xSnxS5I can achieve a maximum value of 3.49 × 10−4 S cm−1 at room temperature when x = 0.4, which is over 40-fold that of the pristine Li6SbS5I. The Li symmetric cell with I-rich Li6.4Sb0.6Sn0.4S5I (LSSSI-0.4) electrolyte delivers a stable Li+ plating/stripping behavior over 450 h at a current density of 0.1 mA cm−2. Benefiting from the decent Li-compatibility of LSSSI-0.4, the assembled ASSLB with LiNi0.8Co0.1Mn0.1O2-based composite cathode and Li-metal anode displays good cycling performance. The LSSSI-0.4 electrolyte also possesses excellent moisture stability. ASSLB using the dried LSSSI-0.4 electrolyte still exhibits a well-maintained initial discharge capacity of 184.0 mA h g−1 at 0.1C and an impressive capacity retention rate of 70.6% after 600 cycles at 0.2C. This work offers a feasible option with superior integrated properties to push forward the advancement of high-performance ASSLBs.
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Energy & Environmental Materials
·
2021
·Vol. 5
·期 1
·353-359
·
IF 15.122
Xingyang Du,Hanying Zhang,Xuexia Lan,Bin Yuan,Renzong Hu
Silicon monoxide (SiO) has aroused increased attention as one of the most promising anodes for high-energy density Li-ion batteries. To enhance the initial Coulombic efficiencies (ICE) and cycle stability of SiO-based anodes, a new facile composition and electrode design strategy have been adapted to fabricate a SiO–Sn–Co/graphite (G) anode. It achieves a unique structure where tiny milled SiO–Sn–Co particles are dispersed among two graphite layers. In this hybrid electrode, Sn–Co alloys promoted Li + extraction kinetics, and the holistic reversibility of SiO and graphite enhanced the electrical conductivity. The SiO–Sn–Co/G electrode delivered an average ICE of 77.6% and a reversible capacity of 640 mAh g −1 at 800 mA g −1 , and the capacity retention was above 98% after 100 cycles, which was much higher than that of the SiO with an ICE of 55.3% and a capacity retention of 50%. These results indicated that this was reliable method to improve the reversibility and cycle ability of the SiO anode. Furthermore, based on its easy and feasible fabrication process, it may provide a suitable choice to combine other alloy anodes with the graphite anode.
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ACS Applied Materials & Interfaces
·
2021
·
IF 9.229
Yu Wang,Haifeng Ji,Xiaojie Zhang,Jingjing Shi,Xiaona Li,Xiaoxia Jiang,Xiongwei Qu
Cyclopropenium cationic-based covalent organic polymer (iCP@TFSI) was successfully prepared through the SN2 reaction and ion replacement process, which can be incorporated into the PEO/LiTFSI matrix as a filler. The obtained solid-state polymer electrolytes were utilized for an all-solid-state lithium–sulfur (Li–S) battery. Padding iCP@TFSI into the PEO matrix not only has a positive influence on both the ionic conductivity and the mechanical capacity of solid-state polymer electrolytes but also increases the stability of the lithium metal anode, which essentially improves the overall cycling ability of all-solid-state Li–S batteries. Among the membranes attained, the PEO-10%iCP@TFSI electrolyte displays the best ionic conductivity up to 1.2 × 10–3 S·cm–1 at 80 °C. The symmetrical lithium battery exhibits higher cycle stability (600 h) due to the higher mechanical properties related to more stable lithium metal interfaces. The Li–S battery based on the PEO-10%iCP@TFSI electrolyte exhibits excellent electrochemical performance with better Coulombic efficiency and outstanding cycling stability. Its capacity is maintained at 490 mAh·g–1 after 500 cycles at 1 C with a 0.032% decay rate each cycle, and the Coulombic efficiency is close to 100% during the whole cycling.
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ACS Applied Materials & Interfaces
·
2021
·
IF 9.229
Hui Wang,Mouren Miao,Hui Li,Yuliang Cao,Hanxi Yang,Xinping Ai
Si is being actively developed as one of the most promising high-capacity anodes for next-generation lithium-ion batteries (LIBs). However, low cycling coulombic efficiency (CE) due to the repetitive growth of the solid electrolyte interphase (SEI) film is still an issue for its application in full batteries. Here, we propose a strategy to in situ form an artificial solid electrolyte interphase (ASEI) on the ferrosilicon/carbon (FeSi/C) anode surface by a purposely designed nucleophilic reaction of polysulfides with vinylene carbonate (VC) and fluoroethylene carbonate (FEC) molecules. The as-formed ASEI layer is mechanically dense and ionically conducting and therefore can effectively prevent the electrolyte infiltration and decomposition while allowing Li+ transport across, thus stabilizing the interface of the FeSi/C anode. As a result, the ASEI-modified FeSi/C anode exhibits a large reversible capacity of 1409.4 mA h g–1, an excellent cycling stability over 650 cycles, and a greatly elevated cycling CE of 99.8%, possibly serving as a high-capacity anode of LIBs.
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